全文获取类型
收费全文 | 2286篇 |
免费 | 61篇 |
国内免费 | 7篇 |
专业分类
化学 | 1615篇 |
晶体学 | 39篇 |
力学 | 19篇 |
数学 | 55篇 |
物理学 | 626篇 |
出版年
2022年 | 13篇 |
2021年 | 14篇 |
2020年 | 24篇 |
2019年 | 26篇 |
2018年 | 22篇 |
2017年 | 12篇 |
2016年 | 45篇 |
2015年 | 36篇 |
2014年 | 50篇 |
2013年 | 93篇 |
2012年 | 84篇 |
2011年 | 86篇 |
2010年 | 49篇 |
2009年 | 61篇 |
2008年 | 126篇 |
2007年 | 103篇 |
2006年 | 125篇 |
2005年 | 124篇 |
2004年 | 144篇 |
2003年 | 110篇 |
2002年 | 82篇 |
2001年 | 58篇 |
2000年 | 41篇 |
1999年 | 50篇 |
1998年 | 21篇 |
1997年 | 22篇 |
1996年 | 37篇 |
1995年 | 40篇 |
1994年 | 30篇 |
1993年 | 23篇 |
1992年 | 53篇 |
1991年 | 44篇 |
1990年 | 27篇 |
1989年 | 34篇 |
1988年 | 21篇 |
1987年 | 32篇 |
1986年 | 33篇 |
1985年 | 37篇 |
1984年 | 24篇 |
1983年 | 17篇 |
1982年 | 26篇 |
1981年 | 22篇 |
1980年 | 30篇 |
1979年 | 21篇 |
1978年 | 18篇 |
1977年 | 17篇 |
1976年 | 13篇 |
1975年 | 22篇 |
1974年 | 21篇 |
1973年 | 27篇 |
排序方式: 共有2354条查询结果,搜索用时 31 毫秒
91.
Layer-by-layer assembled multilayer films of titanate nanotubes, Ag- or Au-loaded nanotubes, and nanotubes/nanosheets with polycations 总被引:1,自引:0,他引:1
Aqueous suspensions of hydrothermally synthesized titanate nanotubes and poly(diallyldimethylammonium chloride) (PDDA) have been employed to fabricate multilayer films on various substrates in a layer-by-layer fashion. Atomic force microscopy displays the dense coverage of the substrate surface by the nanotubes. UV-vis absorption spectroscopy confirms the consecutive growth of PDDA/nanotube layer pairs. Single crystalline Ag and Au nanoparticles with narrow size distribution spatially correlating with the nanotubes have been obtained by treating the nanotubes with AgNO(3) or HAuCl(4) aqueous solution followed by chemical reduction. The noble metal nanoparticles show a strong surface plasmon absorption band. A multilayer film construction of the noble-metal-loaded nanotubes has also been achieved. This process has been further extended to the heteroassembly of nanotubes/nanosheets in different layer sequences. 相似文献
92.
(±) - 33,7 - Trimethyl - 2,9 - dioxatricyclo[3.3.1.04,7]nonane 1 and (±) - 3,3,7 - trimethyl - 2,9-dioxatricyclo [4.2.1.04,7]nonane 2 were synthesized. The former was shown to be (±)-lineatin, an ambrosia beetle pheromone. A selective synthesis of (±)-lineatin was devised, which was modified to yield the both enantiomers of lineatin via optical resolution of an intermediate. 相似文献
93.
[reaction: see text] Reaction of gamma-p-toluenesulfonyl-alpha,beta-epoxysilane with alkyl halides and aldehydes followed by treatment with n-Bu4NF affords alpha,beta-unsaturated aldehydes via a Brook rearrangement-mediated tandem process under extremely mild conditions. 相似文献
94.
T Tokumura T Tanaka A Sasaki Y Tsuchiya K Abe R Machida 《Chemical & pharmaceutical bulletin》1990,38(11):3094-3098
The stability and some physicochemical properties of a novel hexapeptide, (Me)Arg-Lys-Pro-Trp-tert-Leu-Leu-OEt (I), with neurotensin activity, were investigated. The degradation of I in aqueous solution was observed as a pseudo-first order reaction. By determining the degradation rate of I at various pH values, it was found that I was most stable at around pH 4. The activation energies of the degradation in aqueous solutions at pH 2.2, 6.1, 7.0 and 8.0 were 16.3, 22.2, 23.9 and 24.2 kcal/mol, respectively. The enzymatic hydrolysis of I was studied in vitro with a porcine liver esterase at 37 degrees C. The degradation of I in this system was observed as a pseudo-first order reaction. The degradation rate of I in the presence of the esterase was about 10000 times larger than the rate in a buffer solution. I in the solid state was stable under 65 degrees C and labilized by strong light and/or high humidity. The pKa1, pKa2 and pKa3 of I were 7.1, 10.0 and 11.3, respectively. The partition coefficients between n-octanol and the buffer solution at pH values ranging from 2 to 11 were measured. The partition coefficient increased with the increase of the pH value. But the value at pH 7.0 was 2.10 x 10(-2), which was very low. The solubility of I in aqueous solution was more than 10 mg/ml. From the results of the powder X-ray diffraction pattern, I in the solid state was found to be amorphous. The dissolution rates in the 1st and 2nd fluid of JPXI at 37 degrees C and 100 rpm were 19.4 and 9.0 mg/cm2.min, respectively. 相似文献
95.
The synthesis of an asymmetric glycocluster 1 has been achieved by coupling of a sugar unit with the β-alanine polypeptide, the principal chain, and combining a carbohydrate chain with the side chain causing it to branch from the N terminal. The synthesis of this side chain multivalent ligands is based on the scaffolding of some ω-amino acid (glycine, β-alanine, and GABA) derivatives. This method facilitated the synthesis of the cluster, of which the length of each unit differs. 相似文献
96.
In this work we report a novel method that can monitor in vivo the salt permeation process into a plant Vigna angularis using two Ag/AgCl electrodes. The method is based on the electromotive force (emf) measurement using two Ag/AgCl electrodes, one inserted into the V. angularis pith cavity and the other placed into saline ([NaCl]=1 M) surrounding the roots. Temporary change of emf ranging from 0 to ca. 0.115 V was measured in vivo using the system, and the possible physiological phenomenon during the period was discussed. 相似文献
97.
Allylation of acetals with allylsilanes is catalyzed by iodotrimethylsilane to give the corresponding homoallyl ethers, with regiospecific transposition of the allyl group. 相似文献
98.
Fujitani T Nakamura I Kobayashi Y Takahashi A Haneda M Hamada H 《The journal of physical chemistry. B》2005,109(37):17603-17607
Adsorption and reactions of NO on clean and CO-precovered Ir(111) were investigated by means of X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HR-EELS), infrared reflection absorption spectroscopy (IRAS), and temperature-programmed desorption (TPD). Two NO adsorption states, indicative of fcc-hollow sites and atop sites, were present on the Ir(111) surface at saturation coverage. NO adsorbed on hollow sites dissociated to Na and Oa at temperatures above 283 K. The dissociated Na desorbed to form N2 by recombination of Na at 574 K and by a disproportionation reaction between atop-NO and Na at 471 K. Preadsorbed CO inhibited the adsorption of NO on atop sites, whereas adsorption on hollow sites was not affected by the coexistence of CO. The adsorbed CO reacted with dissociated Oa and desorbed as CO2 at 574 K. 相似文献
99.
Masaaki?HanedaEmail author Isao?Nakamura Tadahiro?Fujitani Hideaki?Hamada 《Catalysis Surveys from Asia》2005,9(4):207-215
Comprehensive studies combining surface science and real catalyst were performed to get further insight into catalytic active
site and reaction mechanism for NO decomposition over supported palladium and cobalt oxide-based catalysts. On palladium single-crystal
model catalysts, adsorption, dissociation and desorption behavior of NO was found to be closely related to the surface structures,
the stepped surface palladium being active for dissociation of NO. In accordance with this result, the activity of powder
Pd/Al2O3 catalysts for NO decomposition was directly related to the number of step sites exposed on the surface, suggesting that the
step sites act as the catalytic active site for NO decomposition on Pd/Al2O3. NO decomposition over cobalt oxide was found to be significantly promoted by addition of alkali metals. Surface science
study and catalyst characterization led to the same conclusion that the interface between the alkali metal and Co3O4 serves as the catalytic active site. From the results of in situ Fourier transform infrared (FT-IR) spectroscopy and isotopic transient kinetic analysis, a reaction mechanism was proposed
in which the reaction is initiated by NO adsorption onto alkali metals to form NO2− species and then NO2− species react with the adsorbed NO species to form N2 over the interface between the alkali metal and Co3O4. 相似文献
100.
Diversity-oriented organic synthesis (DOS) is a key concept for construction of skeletally diverse small molecule libraries to discover drug-like small molecules. Here, we describe a DOS class to transform a complex 7-oxanorbornene skeleton, which is readily accessible by a tandem Ugi/Diels-Alder reaction, into two heterotricycle skeletons selectively by using tandem ROM/CM/RCM reaction. In the present study, the mode of cyclization is pre-encoded by building blocks used in the complexity-generating tandem Ugi/Diels-Alder reaction. Since variable alkenes can be used in the CM reaction, our approach can be extended to construct both skeleton- and appendage-diverse small molecule libraries. 相似文献